Light-sensitive material containing a polyhalogenated hydrocarbon, an n-vinylcarbazole, and a furfurylidene compound as an image enhancer and stabilizer

ABSTRACT

A non-silver halide light-sensitive material for dry processing containing (a) polyhalogenated hydrocarbon, (b) N-vinylcarbazole, (c) a furfurylidene compound and optionally at least one of the following; hydroquinone, resorcinol, derivatives thereof, a dye or dye bases.

United States Patent [1 1 Yamashita et a1.

[ LIGHT-SENSITIVE MATERIAL CONTAINING A POLYHALOGENATED HYDROCARBON, ANN-VINYLCARBAZOLE, AND A FURFURYLIDENE COMPOUND AS AN IMAGE ENHANCER ANDSTABILIZER [75] Inventors: Hiroshi Yamashita; Nobuyoshi Sekikawa, bothof Asaka, Japan [73} Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Dec. 29, 1971 [21] Appl. N0.: 213,538

[30] Foreign Application Priority Data Dec. 29, 1970 Japan 45/121448[52] US. Cl 96/90 R, 96/115 P [51] Int. Cl G03c 1/52, G030 1/68 Nov. 20,1973 Primary ExaminerNorman G. Torchin Assistant ExaminerWon H. Louie,Jr. AttorneyRichard C. Sughrue et a1.

[57] ABSTRACT A non-silver halide light-sensitive material for dryprocessing containing (a) polyhalogenated hydrocarbon, (b)N-vinylcarbazole, (c) a furfurylidene compound and optionally at leastone of the following; hydroquinone, resorcinol, derivatives thereof, adye or dye bases.

14 Claims, No Drawings LIGHT-SENSITIVE MATERIAL CONTAINING APOLYI-IALOGENATED HYDROCARBON, AN N-VINYLCARBAZOLE, AND A FURFURYLIDENECOMPOUND AS AN IMAGE ENHANCER AND STABILIZER DESCRIPTION OF THE PRIORART There are many patents relating to non-silver halide light-sensitivematerials comprising a combination of an organic halogen compound and anaromatic amine, such as the U.S. Pat. Nos. 3,042,515; 3,042,516;3,042,517; 3,042,518; 3,042,519, etc. The main problem with suchelements is how to fix the element, that is, how to increase thestability of the obtained image and how to remove the light sensitivityremaining at unexposed portions. Usually, unexposed portions aredesensitized by heating or treating with a solvent after the exposure.Mere heating, however, is not sufficient, and treatment with a solventrequires a long period of time and has defects such as toxicity.

Some attempts have been made to solve these prob- I lems. In U.S. Pat.No. 3,082,086 (Japanese Pat. No.

17701/64), a secondary amine is inactivated by the reaction betweenaromatic amine and carboxylic acid anhydride to remove the remaininglight-sensitivity. The anhydride, however, is so liable to be hydrolyzedby moisture in the air that it lacks storage stability.

In Japanese Pat. No. 16,753/70, the remaining light sensitivity isremoved by treatment with an aqueous so lution containing a reducingheavy metal, a wet processing. i

In Japanese Pat. No. 22,941/69, the adduct ofa bisulfite and a compoundcontaining a carbonyl group is used for fixing.

Light-sensitive materials comprising carbon tetrabromide andN-vinylcarbazole are described in U.S. Pat. Nos. 3,476,562; 3,503,745,etc. Fixing processes thereof are known, e.g., in U.S. Pat. No.3,503,742 (Japanese Pat. No. 2,619/68) the unexposed portions aredesensitized by treatment with ammonia. However, ammonia is notpreferred due to its pungent odor and its toxicity.

ln U.S. Pat. No. 3,512,916, fixing is carried out by treatment with anaqueous solution of sodium sulfite, etc., but this is a wet processingand has the defect that treatment requires a long period of time.

The components (a) and (b) are necessary for the combination of thecomponents (a), (b), (e), namely polyhalogenated hydrocarbon,N-vinylcarbazole, and dye or dye base, thus see U.S. Pat. No. 3,503,745.Further, for the combination of the components (a), (b), (d), namelypolyhalogenated hydrocarbon, N- vinylcarbazole, and hydroquinone,resorcin or derivatives see U.S. Pat. No. 3,544,322.

SUMMARY OF THE INVENTION The present invention relates to a dryprocessing non-silver halide light-sensitive material which provides ablack stable image and is characterized by the inactivation of unexposedportions by heating. More particularly, it relates to a light-sensitivematerial having the following composition; (a) polyhalogenatedhydrocarbon, (b) N-vinylcarbazole, (c) furfurylidene compound, andoptionally at least one of (d) hydroquinone, resorcinol and derivativesthereof and (e) a dye or dye base.

The action of ingredients (a) to (e) in the lightsensitive material isbelieved to be as follows.

Ingredient (a) is a photo-activator which produces free radicals or ionsby the action of light. N-

vinylcarbazole (b) reacts with the free radicals or ions DETAILEDDESCRIPTION OF THE INVENTION The fundamental composition of thelight-sensitive material of the present invention is: (a)polyhalogenated hydrocarbon, (b) N-vinylcarbazole, (c) furfurylidenecompound, and optionally at least one of (d) hydroquinone, resorcinoland derivatives thereof, and (e) a dye or dye base.

Preferably Components Mixture Ratio l/(a) 50/ll/50 5/I-I/5 )/(c)/1-1/100 10/1-1/10 )/(d) 1000/1-1/5 200/1 1]; (bm /l1/1 10 /1 10 /1binder/light-sensitive component l/1002 Q[l I/IO -S/ I VN-vinylcarbazole and carbon tetrabromide cause a thermal reactionbecause they form a charge-transfer complex of 1:1, 2:1 etc., and hencethey seem to have a poor storage stability. Therefore, storage stabilitywill be improved by the addition of a substance that prevents such athermal reaction. It is the ingredient (d) that corresponds to suchsubstance.

The dye produced by the photochemical reaction between carbontetrabromide and N-vinylcarbazole is unstable, especially lacking lightfastness. For example, in the case of a sensitive material whereingelatin is used as a binder, there is obtained, immediately afterprocessing, a greenish-blue image with a yellow background, but, in abright room, the whole turns dark brown, and a brown colored imageappears in the background. As is mentioned above, in a light sensitivematerial comprising carbon tetrabromide and N- vinylcarbazole, there arethe two problems of the stability of the image formed and fogging at theunexposed portions. The present invention has solved these problems. Thefogging at the unexposed portions supposedly results from the colorreaction between N- vinylcarbazole polymer and carbon tetrabromide toadd to the reaction between non-reacted materials.

The formation of the N-vinycarbazoles is sufficiently contemplated. Themolecular weights are supposed about from thousands to scores. ofthousands.

It is believed that the fogging at the unexposed portions results fromthe color reaction between one polyvinylcarbazole and carbontetrabromide, and the reaction "of non-reacted materials,N-vinylcarbazole and carbon tetrabromide.

It has been found that a black, stable color developed body can beobtained with increased image density by the addition of the ingredient(c) to this system. The

black image can be obtained by dry processing, which will extend theregions of application of such an element. For example, thelight-sensitive material of the present invention can be used instead ofan usual printing paper comprising silver halide. It has the advantage 5that the treatment thereof is easy due to the dry processing. Besides,in the case of adding the ingredient (d), apart from acting as astabilizer, the unexposed portions can be desensitized by heating to 70150C after imagewise exposure. The temperature range is ID from 40 250C,preferably from 70C 150C. In addition, the unexposed portions are clearwhite, and hence fog density is extremely low. When ingredients (0) and(d) are present, a blackish brown image is obtained with a whitebackground. The image formed hardly changes in a bright room.

When the ingredient (e) is added, the sensitive wave length region isextended to about 700nm.

When a dye base was used, a rise in sensitivity at the intrinsic regionwas encountered. In a non-sensitized system, the light-sensitive regionis up to 480 nm. It was also found that by the addition of theingredient (e) the storage stability of the sensitive material wasremarkably improved.

As the ingredient (a) of the present invention, the followingpolyhalogenated hydrocarbon can be used:

wherein X represents nothing,

-@- megc e ,7 wherein Y and Y represent H or alkyl group, or

thereof, e. g.,

wherein R and R represent H, an alkyl group of one to six carbon atoms,aryl, hydroxyalkyl, benzoyl, acetyl or R represents H, alkyl, halogen,or alkoxy, and n represents an integer of l-4.

, As the stabilizing and spectrally sensitizing ingredient (e), therecan be used dyes or dye bases (which are converted to a dye byoxidation) such as photographic spectral sensitizing dye materials beingin a form selected from a dye form or a dye base form, such asanthraquinone dyes, triphenylmethane dyes, xanthene dyes, acridine dyes,azine dyes, thiazine dyes, cyanine dyes, styryl dyes, etc.

Above dyes are as follows: anthraquinone dyes such as alizaline (C15800), purpurin (C1l037), alizaline cyanin R (Cll064), etc.,triphenylmethane dyes such as malachite green (CI4200), crystal violet(C142555), methyl green (C1684), naphthalene green (Cl735), etc.,xanthene dyes such as rhodamine B (Cl45l70), eosin (C145380),fuluolesein (C1766), rose bengal (C1777), erythrosin (C1773), etc.,acridine dyes such as acridine orange R (CI46005), acridine yellow(C1785), benzo flavine (C1791 acryflavine, etc., azine dyes such assafranine T (C150240), neutral red (C1825), flavinduline O (C1824),etc., thiazine dyes such as methylene blue (C152015), methylene green(C1924), thionine blue 1 (C152025), etc., cyanine dyes such as ethylred, quinaldine red, neocyanine, etc., styryl dyes such as4-(p-dimethylaminostyryl), N- ethylquinolinium iodide, etc.

As a binder, those employed in usual photographic sensitive materialscan be used. High molecular weight materials can be used as a binder aslong as they have a film-forming ability. As examples of such highmolecular weight materials, there are water soluble materials such asgelatin, polyvinyl alcohol, casein, starch, hydroxyethyl cellulose,carboxymethyl cellulose, polyvinyl pyrrolidone, etc., in addition toorganic solventsoluble materials such as vinyl polymers, e.g., vinylchloride, vinylidene chloride, vinyl acetate, etc., acrylate,polystyrene, ethyl cellulose, rubber chloride, vinylidenechlorideacrylonitrile copolymer, cellulose acetate, waxes, and the like.By High molecular weight is meant solid film-forming high molecularweight materials. The molecular weight range is 5,000 to 5,000,000,preferably 20,000 to 5 million.

The present invention will further be explained by the followingExamples.

EXAMPLE 1 N-Vinylcarbazole l g Carbon tetrabromide 0.8 g

Difurfurylidene pentaerythritol 0.1 g are dissolved in this order in 10ml of 1,2- dichloroethane. Thereafter, a filter paper (made by TOYOKAGAKU SANGYO COMPANY, LTD., No. 4) was dipped thereinto, taken up, thendried to prepare a sensitive material. (The operation was carried outunder a red safety lamp for photography. The processes of the imagewiseexposure, heating, etc. are also likewise carried out. The same appliesto all other Examples.) When the sensitive material thus obtained wasimagewise exposed to a 250 W super high pressure mercury lamp for 10seconds at a distance of 30 cm through a photographic negative image,there was obtained a black image with a yellow background. In the caseof the combination of N-vinylcarbazole and carbon tetrabromide, theimage obtained was light grayish green. By the addition ofdifurfurylidene penataerythritol, the image density increased by about0.3.

EXAMPLE 2 In the same manner as in Example 1 using the followingfurfurylidene azine instead of difurfurylidene pentaerythritol, therewas prepared a light-sensitive material, which was imagewise exposed toa 250 W super high pressure mercury lamp for 10 seconds at a distance of30 cm through photographic negative image, and then heated to 100C toobtain a black image.

EXAMPLE 3 An acetone solution containing 5 g of N- vinylcarbazole wasadded to 50 ml ofa 16 percent gelatin aqueous solution, then. stirred athigh speed at a temperature of 70C for 2 minutes with the use of ahomomixer (made by TOKUEHU KIKA KOGYO COMPANY, LTD.) to finely dipersethe N- vinylcarbazole in the gelatin. Thereafter, dichloroethanesolution containing 4 g of carbon tetrabromide and 0.5 g ofdifurfurylidene pentaerythritol was added thereto and emulsified anddispersed in the same manner. The resulting emulsion was coated onto abaryta paper and dried to prepare a sensitive material, which wasimagewise exposed to a 250 W super high pressure mercury lamp for 10seconds at a distance of 30 cm through a photographic negative image.

When the sensitive material was imagewise exposed to a 300 Wincandescent lamp for l seconds at a distance of 35 cm through aphotographic positive image, then the element exposed to a 250 W superhigh pressure mercury lamp for 10 seconds at a distance of 30 cm, therewas obtained a black image thereon with pale yellow background.

EXAMPLE 4 N-Vinylcarbazole 5 g Carbon tetrabromide 4 g Difurfurylidenepentaerythritol 0.5 g

Crystal violet 2 mg were dispersed in the same manner as in Example 3 toprepare a sensitive material. The resulting sensitive material wasimagewise exposed to a 300 W photographic flood lamp through a filterwhich transmits light of a wave length longer than 600 nm and through aphotographic positive image for sec. Then the element was exposed to a250 W super high pressure mercury lamp for 10 seconds at a distance of30 cm to obtain a black image thereon.

EXAMPLE 5 N-Vinylcarbazole 5 g Carbon tetrabormide 4 g Difurfurylidenepentaerythritol 0.5 g

4-(P-dimethylaminostyryl)quinoline l g were dispersed in the same way asin Example 3 to prepare a sensitive material. The resulting material wasimagewise exposed to a 300 W incandescent lamp through photographicpositive image for 0.5 second at a distance of 35 cm, the whole surfacethereof was then exposed to a red lamp which emits light of wavelengthslonger than 600 nm for 5 seconds and finally surface thereof exposed toa 250 W mercury lamp for 10 seconds at a distance of 30 cm to obtain ablack image with a pale yellow background.

EXAMPLE 6 Example 5 was duplicated except that polyvinyl alcohol wasused instead of gelatin. After a processing as in Example 5, there wasobtained a black image with a pale yellow background.

EXAMPLE 7 N-vinylcarbazole 1 g Carbon tetrabromide 0.8 g

Difurfurylidene pentaerythritol 0.1 g

Dichloroethane 2 ml are disolved in a 15 percent benzene solution ofpolystyrene. In this case, dichloroethane is used in order to dissolvethe difurfurylidene pentaerythritol. The resulting solution was coatedonto a baryta paper and than dried. The sensitive material thus obtainedwas imagewise exposed to a 250 W super high pressure mercury lampthrough photographic negative image for 10 seconds at a distance of 30cm, andwas successively exposed to a 375 W infrared lamp for 30 secondsat a distance of 22 cm to obtain a black image thereon with a paleyellow background.

For comparison,

N-Vinycarbazole l g Carbon tetrabromide 0.8 g were dissolved in a 15percent by weight polystyrene in benzene solution, and a photosensitivematerial was prepared in the same manner as in Example 7. When theresulting photosensitive material was imagewise exposed to a mercurylamp and an infraredlamp in the same way as in Example 7, there wasobtained a blue image. In this case, when exposure to infrared rays wasconducted for a long time, the image turned green and finally brown.

EXAMPLE 8 N-Vinylcabazole l g Carbon tetrabromide 0.8 g

Difurfurylidene pentaerythritol 0.1 g

Hydroquinone derivative (one of the four listed below)0.l g

4 were dissolved in 10 ml of dichloroethane, and a photosensitivematerial was prepared in the same manner as in Example 1. As thehydroquinone derivatives, hydroquinone, hydroquinone monomethylether,dimethoxybenzene or P-bis(Z-tetrahydropyranyloxy) benzene were used. Thephotosensitive materials obtained were exposed to a 250 W mercury lampfor 5 seconds at a distance of 30 cm, then heated to C. for 30 secondsto obtain a blackish-brown image thereon with a white background.

EXAMPLE 9 Example 8 was duplicated except that a resorcinol derivativewas used instead of a hydroquinone. As the resorcinol derivatives,resorcinol, 4-ethylresorcinol, resorcinol monobenzoate or phloroglucinwere used. The resulting photosensitive materials were imagewise exposedto a mercury lamp and heated in the same manner as in Example 8, andthere was thus obtained a blackish-brown image thereon with a whitebackground.

EXAMPLE l N-Vinylcarbazole 1 g Carbon tetrabromide 0.5 g

l-lexachloroethane 0.5 g

Difurfurylidene pentaerythritol 0.1 g

Chloroform 2 ml were dissolved in ml of percent ethyl acetate solutionof polymethyl methacrylate, a photosensitive material was prepared andprocessed in the same manner as in Example 7 to obtain a black imagewith pale polles background.

EXAMPLE 1 I N-Vinylcarbazole l g Iodoform 0.5 g

Difurfurylidene pentaerythritol 0.1 g

Chloroform 2 ml were dispersed in gelatin to prepare a photosensitivematerial in the same manner as in Example 3. The resultingphotosensitive material was exposed to 250 W super high pressure mercurylamp imagewise at a distance of cm to obtain a black image thereon.

EXAMPLE l2 utes to obtain a blackish-brown image thereon with a whitebackground. The unexposed part thereof did not color when left in abright room.

EXAMPLE l3 N-Vinylcarbazole 5 g Carbon tetrabromide 4 g Difurfurylidenepentaerythritol 0.5 g P-bis(Z-tetrahydropyranyloxy)benzene 0.1 g4-(P-dimethylaminostryl)quinoline 1 mg were dispersed in gelatin and aphotosensitive material was prepared in the same way as in Example 3.The resulting photosensitive material was processed in the same manneras in Example 5 to obtain a black image thereon with pale yellowbackground.

Whatis claimed is:

1. A non-silver halide light-sensitive material for dry processing,containing the ingredients (a) polyhalogenated hydrocarbon, )b)N-vinylcarbazole and (c) furfurylidene compound; said ingredient (a)being the compound represented by the following formula:

wherein R represents H, X, COOR', or -C(H);; ,.X,,;-

R being a hydrogen atom, methyl group or ethyl group; X represents Cl,Br or I; and n and m represent an integer of 2 or 3; said ingredient (c)being the compound represented by the following formula:

wherein X represents nothing,

wherein Y and Y' are a hydrogen atom or alkyl group, for the compoundrepresented by the following formula:

1 o-oHl cm-o on C \CH O 0 said ingredient (c) being present in an amounteffective to increase the developed image density to blacken said imageand to stabilize said image to increase its light fastness.

2. The non-silver halide light-sensitive material as claimed in claim 1wherein said material further contains at least one additional compoundof the ingredient (d) and ingredient (e); said ingredient (d) beinghydroquinone, resorcinol or derivatives thereof, represented by thefollowing formulas:

OR OR wherein R and R are a hydrogen atom, an alkyl group having one tosix carbon atoms, an aryl group, a hydroxyalkyl group, a benzoyl group,an acetyl group or R" represents a hydrogen atom, alkyl group having oneto six carbon atoms, hydroxyl group, halogen atom or alkoxyl group and nrepresents an integer of l to 4, and ingredient (e) being a photographicspectral sensitizing dye material in a dye or a dye base form.

3. The light-sensitive material of claim 1 wherein the ratio of theamount of ingredient (b) to that of ingredient (c) is between to 1 and lto 100.

4. The light-sensitive material of claim 3 wherein the ratio of theamount ofingredient (b) to that of ingredient (a) is between 50 to l andl to 50.

5. The light-sensitive material of claim 2 in which the ratio of theamount of ingredient (b) to that of ingredient (d) is between 1,000 to land l to 5 and in which the ratio of the amount of ingredient (b) tothat of ingredient (e) is between 10 to l and I to l.

6. The light-sensitive material of claim I further comprising a bindermaterial.

7. The light-sensitive material of claim 6 wherein the ratio of theamount of binder material to that of the remaining ingredients of saidlight-sensitive material is between 1 to 100 and 20 to l.

8. The light-sensitive material of claim 4 whereinthe ratio of theamount of ingredient (b) to that of ingredient (a) is between 5 to l andl to 5 and the ratio of the amount of ingredient (b) to that ofingredient (c) is between to l and l to 10.

9. The light-sensitive material of claim 5 wherein the ratio of theamount of ingredient (b) to that of ingredient (d) is between 200 to land l to 2 and the ratio of the amount of ingredient (b) to that ofingredient (e) is between 10 to 1 and 10 to 1.

10. The light-sensitive material of claim 1 wherein said ingredient (a)is carbon tetrabromide and said ingredient (c) is difurfurylidenepentaerythritol.

11. The light-sensitive material of claim 2 wherein said ingredient (d)is P-bis (2-tetrahydropyranyloxy) benzene and said ingredient (e) is4-(p- 10 dimethylaminostyryl) quinoline.

12. The light-sensitive material of claim 1 wherein said ingredient (a)is capable of acting as a photoactivator which produces free radicals orions by the action of light, said ingredient (b) is capable of reactingwith said free radicals or ions produced by ingredient (a) to producecolor and said ingredient (c) is capable of stabilizing and increasingthe density of an image formed by the reaction of said ingredients (a)and (b).

13. The light-sensitive material of claim 2 in which R" is an ethylgroup.

14. The light-sensitive material of claim 1 in which Y and Y represent ahydrogen atom or alkyl group having from one to six carbon atoms.

2. The non-silver halide light-sensitive material as claimed in claim 1wherein said material further contains at least one additional compoundof the ingredient (d) and ingredient (e); said ingredient (d) beinghydroquinone, resorcinol or derivatives thereof, represented by thefollowing formulas:
 3. The light-sensitive material of claim 1 whereinthe ratio of the amount of ingredient (b) to that of ingredient (c) isbetween 100 to 1 and 1 to
 100. 4. The light-sensitive material of claim3 wherein the ratio of the amount of ingredient (b) to that ofingredient (a) is between 50 to 1 and 1 to
 50. 5. The light-sensitivematerial of claim 2 in which the ratio of the amount of ingredient (b)to that of ingredient (d) is between 1,000 to 1 and 1 to 5 and in whichthe ratio of the amount of ingredient (b) to that of ingredient (e) isbetween 105 to 1 and 1 to
 1. 6. The light-sensitive material of claim 1further comprising a binder material.
 7. The light-sensitive materiAl ofclaim 6 wherein the ratio of the amount of binder material to that ofthe remaining ingredients of said light-sensitive material is between 1to 100 and 20 to
 1. 8. The light-sensitive material of claim 4 whereinthe ratio of the amount of ingredient (b) to that of ingredient (a) isbetween 5 to 1 and 1 to 5 and the ratio of the amount of ingredient (b)to that of ingredient (c) is between 10 to 1 and 1 to
 10. 9. Thelight-sensitive material of claim 5 wherein the ratio of the amount ofingredient (b) to that of ingredient (d) is between 200 to 1 and 1 to 2and the ratio of the amount of ingredient (b) to that of ingredient (e)is between 105 to 1 and 103 to
 1. 10. The light-sensitive material ofclaim 1 wherein said ingredient (a) is carbon tetrabromide and saidingredient (c) is difurfurylidene pentaerythritol.
 11. Thelight-sensitive material of claim 2 wherein said ingredient (d) is P-bis(2-tetrahydropyranyloxy) benzene and said ingredient (e) is4-(p-dimethylaminostyryl) quinoline.
 12. The light-sensitive material ofclaim 1 wherein said ingredient (a) is capable of acting as aphotoactivator which produces free radicals or ions by the action oflight, said ingredient (b) is capable of reacting with said freeradicals or ions produced by ingredient (a) to produce color and saidingredient (c) is capable of stabilizing and increasing the density ofan image formed by the reaction of said ingredients (a) and (b).
 13. Thelight-sensitive material of claim 2 in which R'''' is an ethyl group.14. The light-sensitive material of claim 1 in which Y and Y'' representa hydrogen atom or alkyl group having from one to six carbon atoms.